Ketone resins



Patented Nov. 6, 1945 KETONE nnsms Vernon E. Haury, El 'Gerrlto, Calif assl znor to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application March 3, 1944, Serial No. 524,952

20 Claims. (01. 260-64) This invention relates to ketone resins and to a process for their manufacture. More particularly, the invention deals with a novel class of ketone resins prepared by reacting an aldehyde with unsaturated cyclic ketones of a particular type.

It is an object of the present invention to provide a method for converting a class of higher ketonesinto valuable resinous materials. Another object is to provide a method of reacting these higher ketones with aldehydes in a manner which permits high yields of thermoplastic ketone resins with valuable and unusual properties not possessed by ketone resins prepared heretofore.

I have discovered that these and other objects of the invention. which will be apparent from the following description, are accomplished by condensing a particular type of cyclic and unsatuated ketones with an aldehyde in the presence of a condensing catalyst and of a substance rendering the. reaction mixture homogeneous. Further, it was found that since the ketones are cyclic and contain at least two oleflnic double bonds per molecule, the resins which are obtained have the property of changing their solubility characteristic upon being contacted with oxygen, which property is particularly useful and valuable in a resinous material. In general, the resins of the invention are hard, reddish colored thermoplastics which are soluble in common organic solvents.

The unsaturated cyclic ketones converted to resins by the method 01 the invention are substituted cyclohexen-2-ones having at least one olefinic linkage present in a side chain or side chains linked to the cyclohexenone ring. The exact structure or chemical configuration of these unsaturated ketones is not known, although it is recognized that they are unsaturated mono ketones which are substituted cyclohexenones with an olefinic linkage present in the ring probably in the A position and with at least one olefinic linkage contained in a side-chain or additional ring linked to the cyclohexenone ring. These unsaturated cyclic ketones thus contain at least two olefinic linkages and the presence in the compounds of this unsaturation, coupled with their cyclic character, is responsible for the resins obtained by condensing the ketones with aldehydes to absorb or combine with oxygen so as to cause the valuable change in solubility. characteristics.

The simplest member of the class of unsaturated ketones are termed xylitones by the art. The xylitones, of which there are several isomeric compounds, are tetramer condensates of acetone of the formula C12H1a0. In addition to the xylitones, other higher auto-condensation products of acetone are suitable, such as condensates tones which are at least tetramers of such ketones are also used in obtaining the resinous products by condensation with aldehydes. Such unsaturated ketones include what may be termed the homoxylitones of methyl ethyl ketone, the homozylitones of methyl propyl ketone, the homoxylitones of diethyl ketone, etc., all of which are tetramer auto-condensates of the parent, lower ketones. If desired, the higher and more complex auto-condensates can be employed such as the pentamer, hexamer, heptamer, etc, These unsaturated ketones are crotonaldehyde-type of autoor self-condensation products of lower aliphatic ketones and are products or by-products obtainable by certain methods of condensation which are described in U. S. Patent 2,309,650 and copending application, Serial No. 474,060, filed January 28, 1943.

In this application, the terms tetramer, pentamer, hexamer," etc., refer to the number of molecules of a .lower ketone which have been combined to form a molecule of auto-condensate by crotonaldehyde-type of condensation. Thus xylitone, .which is formed by condensation of four molecules of acetone to form a molecule of the product, is termed the tetramer autocondensate of acetone and, for convenience and lack of a better name, the product obtainable by combination of live molecules of acetone is referred to as the pentamer auto-condensate of acetone. Similarly, the auto-condensate from six molecules of other ketones than acetone such as methyl ethyl ketone is termed the hexamer auto-condensate of the parent ketone. These terms are used to indicate the character of the higher auto-condensation products wherein the exact configuration of the atoms or chemical structure is unknown.

The lower aliphatic ketones employed in forming the unsaturated ketones by crotonaldehydetype of auto-condensation include such representative compounds as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, diethyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl pentyl ketone, dipropyl ketone, ethyl butyl ketone, and methyl heptyl ketone. In addition, intermediate autocondensates like mesityl oxide can be subjected to crotonaldehyde-type of condensation to yield -12 carbon atom xylitone'aswell as higher multialdol-type of condensation which involves couhyde group is linked directly to a member of the pling of two molecules of acetaldehyde with no class consisting of the hydrogen atom and mono.- formation or elimination of a molecule of water valent hydrocarbon radicals. Besides the free in the reaction which gives a molecule of aldol. uncombined aldehydes, polymers of the aide- The formation of the substituted A -cyclohexe hydes, which are capable of giving free aldehydes nones also involves cyclization as well as crotonunder the resin-forming conditions, can be used aldehyde-type of auto-condensation. such as para-formaldehyde, para-aldehyde.

While the resin treated according to the presmeta-aldehyde, and the like. ent invention has been described as being formed In order to effect the reaction between a higher by reaction of an aldehyde with a single substiketone and an aldehyde, it is necessary to place a tuted A -cyclohexenone of the indicated class, the mixture. of the reactants in contact with a conresin can be formed from mixtures of the ketones densing agent or catalyst. For this purpose, including structural isomers within the class as any condensing agent can be employed although well as mixtures which contain different numbers some types are more preferable than others. An of carbon atoms. amount of from about, 0.5 to 5 per cent by weight All of the Class Of unsaturated etones which of the reactants is used. The preferred catalysts are tetramer or higher auto-condensates of lowinclude strong basic condensing agents such as er aliphatic ketones have in common the charthe hydroxides, oxides and a-lcoholates .of the acteristic structure of being substituted a -cycloalkali metals as well as strong organic bases like hexenones. While the higher compounds arenot the quaternary ammonium bases. Other less simply homologues of xylitone and homoxylitone, basic agents may be used if desired such as the the class does possess an orderly regularity of alkaline earth hydroxides and oxides. In some structure. This may be illustrated by considercases it may be advantageous to employ acidic ation of the auto-condensates of acetone, methyl substances such as sulfuric acid, hydrochloric ethyl ketone and methyl propyl ketone given in acid, phosphoric acid, telluric acid, tungstic acid the following table together with the general forand the like as well as acid salts such as sodium mula for each series wherein m is an integer of 4 acid sulfate, etc. The catalysts may be employed to 10 and n is related to m by the indicated equain the reaction mixture per se or, if desired, they tion. 4 may be used as a solution with a solvent. Suit- Auto-condensate Acetone ggggg g g gg Tetramer CHHIBO 015E150 CaoHnO H C HnO CuHn u uO Cao wO CuHuO Etc. Etc.

Decamer 030E410 Formula of the series o.nm..+l o Q.Hz(s-+1)O ouiuhmo wherein m a an integer oi 4 to 10 and n=3m n=4m. n=5m pie-unsaturated products containing 18, 24 and 30 carbon atoms which are substituted A -cyclohexenones. Condensation of homomesityl oxides of the other lower aliphatic ketones are similarly suitable. By crotonaldehyde-type of condensation used in this specification reference is made to that type of condensation which occurs when two molecules of acetaldehyde couple with elimination of a molecule of water forming a molecule of crotonaldehyde as distinguished from quality than with other aldehydes. However, other aldehydes may be used, if desired, such as acetal'dehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeric aldehyde, ethylhexanal. acrolein, crotonaldehyde, benzaldehyde, paramethylbenzaldehyde, ortho-tertiary butyl benzaldehyde, and the like, together with their homologues, analogues'and suitable substitution products. In general, the aldehyde reactant used in the process is an aldehyde wherein the alde- Preferably the unsaturated ketones contain not more than 30 carbon atoms and the most preferred compounds are the tetramers and pentamers of lower aliphatic ketones. The unsaturated ketones of the class are of the formula CnHz(m(r-1)+1)O wherein m and k are each integers with m of 4 to 10 and k of 3 to 9 and n=kX m. In this general formula, n is related to the number of carbon atoms in the ketone and is at least 12 while It represents the number of carbon atoms in the parent ketone from which the auto-condensate is derived. Further, m is the measure of degree of condensation (m equals 4 with the tetramer, 5 with the pentamer, etc.).

The substituted A -cyclohexenones of the class indicated are converted into resinous materials by reaction with an aldehyde. For this purpose formaldehyde is a most preferred reactant in that this substance is more reactive and gives higher yields while the products are of better able organic solvents may be employed for this purpose. Particularly suited are aqueous solutions of the alkali metal hydroxides, the quaternary ammonium bases, the acids and the acid salts.

The higher ketones employed as starting materials in the process are substantially insoluble in water and in aqueous solutions of the aldehydes such as an aqueous solution of the most preferred reactant, formaldehyde. In order that the reaction between the ketones and aldehydes be effected readily, it is desirable that the reaction mixture be in a homogeneous state, i. e., that the reactants and catalyst be in a solution comprising a single phase, at least at the start and early part of the reaction. To this end, a homogenizing solvent is employed in the reaction mixture. In the absence of a homogenizing solvent, the yield of resin is very low. Many solvents are suitable for this purpose and the choice of a particular solvent will depend upon the particular reactants employed, the catalyst used and the presence or absence of water in the mixture. The lower aliphatic alcohols such as methanol, ethanol, isopropanol, etc., are particularly suitable homogenizing solvents. The amount of these homogenizing solvents employed will depend upon the character of the reaction mixture. In general, sufiicient homogenizing solvent is used so that the reaction mixture is homogeneous at least when first heated.

The homogenizing solvent may serve a twofold purpose in the process. Besides rendering the reaction mixture homogeneous, it may also be used to regulate the temperature of the reaction mixture during the heating thereof since ordiassauo' homogenizing solvent, condensation catalyst and unreacted materials, and then subject the separated resin to the action of heat under anhynarily the reaction is eflected at not overly high temperatures. By heating the reaction mixture in a vessel fitted with a reflux condenser, the temperature may be made to reach and hold the boiling temperature of the mixture and this will be largely dependent upon the refluxing temperature of the homogenizing solvent especially after the reaction has progressed to a considerable extent with substantially no other lower boiling constituents remaining in the mixture. To effect the desired reaction, temperatures, in general, between about 50 C. and 150 C. are employed.

While temperatures of from about 50 C. to 150 C. are preferred for eifecting the condensation to form the resin, higher temperatures can be used if desired. Thus, the reaction mixture containing the reactants, catalyst solution and homogenizer, can be heated in a closed pressure vessel at a temperature between 150 C. and 300 C. in order to convert the ketones to resins. In general, however, temperatures within the preferred range are most desirable since the resins obtained in this manner are lighter in color than those prepared at thehigher temperatures.

Upon completion of the resin-forming conden-- low-boilingproducts, and secondly at reduced.

pressures to remove higher-boiling products from the ketone resin. By completing the distillation operation at very low pressures of 1 to 10 mm. of Hg and at temperatures between about 150 C. and 250 C., but below a temperature at which appreciable thermal decomposition of the resin occurs, the resin is obtained in a hard, brittle,

desirable form. Besides the above-outlined scheme of recovery of the resin, other methods may be employed, if desired, such as fractional precipitation, extraction and the like.

It has been found that subjecting the resinous materials to the distillation operation serves a two-fold purpose; one, volatile materials associated with the resins are removed and two, the subjecting of the resins to the action of heat after removal of the condensation catalyst cures the resins, which eifect is manifested by an increase in the softening point. In some cases it is desirable to separate the resin from the other constituents of the reaction mixture suchas the drous conditions using a temperature of 150 C. to 250 C. whereby the softening point of the resin is increased by the treatment. This curing operation does not in general cause the resins to set to an insoluble and infusible state. In other words, the resins of the invention prepared from saturated aldehydes are not thermo-setting, but rather, are thermoplastic although they are subject to curing by heat which causes their softening points to be raised. Although the softening point of the resins is increased by heating the initial reaction mixture at the higher indicated temperatures, this procedure is undesirable since the presence of the catalyst at the high temperature causes the resins to become more discolored than when the heating is done after removal of the catalyst.

. The unique resins of the invention prepared from higher ketones containing at least two olefinic double bonds in the molecule combine with or absorb oxygen and may be converted to the less-soluble form by contact with oxygen. A suitable method of converting the resins is to dissolve them in a suitable solvent and pass on oxygen-containing gas such "as air through the solution. The rate of absorption of oxygen by the resins is increased in the presence of a siccative and heat and, if desired, the resins may be changed to the less-soluble form more rapidly by incorporating in them driers such as lead.

manganese and/or cobalt naphthenates, linoleates, resinates and other like-acting substances.

The resins are very useful substances. They may be employed in coating compositions, impregnating compositions, film-forming compositions and the like as well as for electrical insulation, manufacturing molded articles and nu- "merous other miscellaneous uses.

The following examples are given for the purpose of illustrating various details of the invention, but are not to be construed as limitative:

Example I About 1240 ms'or xyntone (01211180) and 565 gms. of -3'7 aqueous formaldehyde were homogenized with 1100 gms. of methanol to which was added sodium hydroxide (0.5% of total charge) in the form of its 30% aqueous solution. The mixture was warmed cautiously, an exothermic reaction taking place, and finally refluxed for a period of three hours. The methanol was distilled from the mixture and the residue washed with water to remove caustic. Unreacted ketone was then separated by vacuum distillation. The product weighing about 850 gms. was obtained as the residue from this distillation and solidified on cooling to a brittle resin. The physical properties of a sample of the resin were as follows:

Per cent-carbon 79.5 Per cent-hydrogen Q. 9.3 Mol. wt 600 M. P., C. (Mercury) 70 Color -Orange to red, E to H (rosin scale) Example II About gms. of 'xylitone (B. R. -112.5 C. at 10 mm.), 32 gms. of acrolein, and suflicient methanol to render the mixture homogeneous, to gether with 0.5% sodium hydroxideas its 30% aqeous solution, were refluxed for about 2 hours.

The resin layer which formed during the heating A ketone resin was prepared from a mixture of isomeric substituted n -cyclohexenones of the formula CmHazO having a boiling range of 142 C. to 175 C. at 10 mm. pressure. The ketone mixture was obtained as a higher boiling by-product from preparation of isophorone by crotonaldehyde-type auto-condensation of acetone with aqueous potassium hydroxide in liquid phase at about 170 C. r

A mixture of about 250 gms. of the ketone, 166 gms. of 36% aqueous formaldehyde, and sumcient methanol (about 300 gms.) to render the reaction mixture homogeneous, to which was added sodium hydroxide in amount of 0.5% of the total mixture, was heated at reflux temperature for about 3 hours. The reaction mixture was then cooled, the catalyst neutralized and the resin layer separated. The separated layer was washed several times with hot water and distilled to 180 C. at 2 mm. pressure. About 80 gms. of unreacted ketone was recovered by the distillation while about 193 gms. of the thermoplastic ketone resin remained as residue. The resin had a color of D on the Rosin scale and a softening point of about 78 C.

Example 1V About 178 gms. of xylitones (C12H1s0) obtained by crotonaldehyde-type auto-condensation of mesityl oxide was mixed with 81 gms. of 37% aqueous formaldehyde solution. To this mixture was added approximately 5 gms. of 30% aqueous sodium hydroxide solution and about 95 gms. of methanol which rendered the mixture homogeneous. The mixture was contained in a flask fitted with a reflux condenser and upon heating the contents of the flask, the temperature of the mixture remained at about 76 C. owing to the refluxing of the methanol therein. The mixture remained homogeneous for about /2 hour after which two liquid phases separated. The heating was continued over a total period of about 3 hours. The mixture was then cooled, brine added and the resin phase extracted with ether. The ether was dried with anhydrous sodium sulphate and the ether distilled therefrom. The remaining oil was then distilled in vacuo and after removal of the distillable material, about 106 gms. of a reddish, brittle, transparent resin was obtained. This resin had a color corresponding to E on the rosin color scale and was soluble in alcohols, ketones, esters, aromatic hydrocarbons and paraiiinic hydrocarbons. A cryoscopic determination in glacial acetic acid indicated the molecular weight was about 530. Exposure of the resin to the action of air increased its oxygen content and changed it to a form which was insoluble in parafiinic hydrocarbons.

The presence of the homogenizer in the reaction mixture is essential to obtaining a practical rate of resin formation. With a reaction mixture containing the same amount of identical reactants, but in the absence of the homogenizer, methyl alcohol, which was treated under the same conditions as in the preceding example, the quantity of resin amounted to less than one gram.

Example V A mixture containing about 258 gms. of cylic unsaturated ketones having the formula CraHaoO prepared by erotonaldehyde-type auto-condensation of mesityl oxide, about 83 gms. of 36% aqueous formaldehyde solution, and about 0.5% of sodium hydroxide in the form of an aqueous solution was prepared. To this mixture was added about 170 gms. of methanol to make it homogeneous and the mixture was then heated for approximately three hours at a temperature of 65i5 C. The resin formed was recovered in a similar manner to that described in Example III. The resin had a color of E on the Rosin scale and softened at C.

Example VI Approximately 169 gms. of substituted A- oyclohexenones of the formula 02411340 from condensation of mesityl oxide, about 42 gms. of 36% aqueous formaldehyde solution, and 0.5% sodium hydroxide as aqueous solution together with about 325 gms. of methanol were heated at a temperature of 65 15 C. for three hours. About 169 gms. of light red brittle resin was recovered from the reaction mixture which was slightly darker in color than that described in Example V.

Example VII A mixture of isomers of substituted A -cyclohexenone of the formulas CizHuO (xylitone) and C15H22O which had a boiling range of C. to C. at 10 mm. was reacted with formaldehyde to give a resin. About 100 gms. of the ketone, 82 gms. of 36% formalin, and sufllcient Example VIII A mixture of about 100 gms. of ketone (the same as that described in Example VII), 89 gms. of 36% formalin, sufficient methanol to render the mixture homogeneous, and 0.5% sodium hydroxide based on the total weight of the mixture, was heated in a nickel bomb for 1 hours at 140 C. to C. The atalyst was neutralized and the resin layer separated. In order to determine the effect of avoiding the high temperature used in removing unreacted ketone which cures the resin and increases its softening point,

the separated layer was steam distilled to remove the unreacted ketone. In this manner, about 24 gms. of ketone was recovered. The resin obtained in an amount of about 64 gms. was dark red in color and soft and sticky in consistency. By subjecting the resin to temperatures of C. to C. after its initial formation, it can be converted to a hard material of satisfactory softening point.

Example IX Tetra ethyl ammonium hydroxide was tested as a polymerization catalyst by heating a mixture consisting of about 178 gms. of xylitones described in Example I, 81 gms. of 37% aqueous atmospheric pressure. The distillable material at Example X A. mixture containing about 178 gm. of xylitones from condensation of mesityl oxide, 30 gm. of formaldehyde in the form of a 37% aqueous solution, gms. of 96% sulfuric acid, and sufflcient methanol to homogenize the mixture was heated at refluxing temperature for approximately three hours. The resin which was recovered was dark red in color.

Example x1 A crude mixture of cyclic unsaturated ketones was converted into a resin. The ketone mixture boiled at 110 C. to 175 C. at mm. pressure and consisted 'of various isomeric compounds of the formula Cal-11.0 and 015K220 which were substituted n -cyelohexenones.

About 250 gms. oi the ketone, 186 gms. of 36% formalin, 35 ms. of 30% aqueous sodium hy-' droxide and suflicient methyl alcohol to homogenize, were heated at reflux temperature for 3 hours. The catalyst was neutralized, the resin layer separated and then subjected to distillation in vacuo for recovery of about 42 gms. of unreacted ketone. About 250 gm. of resin was obtained whichwas of color F on the Rosin scale and had a softening point of 85 C. on a hot plate.

Example XII A mixture was prepared containing about 178 ms. of xylitones from condensation of mesityl oxide, 200 gm. of methanol, and 5 gms. of 30% aqueous sodium hydroxide solution. To this mixture there was added about 44 gms. of acetaldehyde in 100 gms. of methanol in the course of 15 minutes while maintaining the temperature at about 15 C. The entire mixture was then heated for about 3 hours at a refluxing temperature oi about 69 Q. The product'was water-washed and distilled. The resin obtained amounted to about 38 gms. and was a dark red, brittle solid with the followlngisolubility characteristics: 7

Solvent Cold Hot -1 v thinner 11 3 0. Slightly soluble.

oluble.

Do. Do.

Example XIII Approximately 178 ms. of xylitones from condensation of mesityl oxide, 106 ms. of benzaldehyde, 4 gms. of 30% aqueous sodium hydroxide solution, and 150 ms. of methanol were heated at about 72 C. for 5 hours. The reaction product was washed with water and distilled under subabout 215 C. under 1 mm. pressure was removed and about 11 ms. of dark red resin remained. This resin was soluble in P and V thinner, ketones, alcohols higher than methanol and slightly soluble in methanol.

Examples XIV Samples of resin prepared from mesityl oxide condensate and formaldehyde were given the treatment indicated in the following table and were analyzed thereafter:

The results obtained from the experiments demonstrate the ability of the resin to, absorb oxygen.- Furthermore, the fact that the ratio of carbon to hydrogen preciable removal of carbon or hydrogen therefrom.

This application is a co'ntinuation-in-part of my copending application, Serial No. 337,686, filed May 28, 1940.

I claim as my invention:

1. A process for the production of ketone resins which comprises heating a substituted A -cyclohexenone with an aldehyde wherein the aldehyde group is linked directly to a member of the class consisting of the hydrogen atom and monovalent hydrocarbon radicals, said heating being effected with the reactants in the presence of a condensing agent and suflicient organic homogenizing solvent to render the reaction mixture homogeneous at least when first heated and said substituted A cyclohexenone being an auto-condensation product of an aliphatic ketone and of the formula CnHa m 1 =-l +1)O wherein m and k are integers with m or 4 to 10 and 1c of 3 to 9 and n=k m.

2. A process for the production of ketone resins which comprises heating a substituted n -cyclohexenone with formaldehyde in the presence of a basic-acting condensing agent and suflicient methyl alcohol to render the reaction mixture homogeneous at least when first heated, said substituted n -cyclohexenorle being an auto-condensation product or an aliphatic ketone and of the formula CnH:(m(l-l)+l 0 wnerem m and lo are integers with m of at least 4 and 1c of at least 3 and n=icxm but not more-than 30.

3. A process for the product on of ketone resins which comprises heating formaldehyde with a substituted A -cyclonexenone auto-condensation product of acetone of the formula CnH2(2m+i)O wherein m is an integer of 4 to 10 and n=3m, said heating being effected with the reactants in the presence of an alkali metal hydroxide and suflicient organic homogenizing solvent to render. the

reaction mixture homogeneous at least when first heated.

4. A process for the production of ketone resins which comprises heating formaldehyde with a substituted Ai-cyclohexenone auto-condensation product of acetone of the formula CnH2(2m+1)O wherein 'm is an integer of at least 4 and n=-3m but is not greater than 30, said heating being effected with the reactants in the presence of an alkali metal hydroxide and sufilcient methyl alcohol to render the reaction mixture homogeneous at least when first heated.

' perature of 150 5. A process for the production of ketone resins which comprises heating formaldehyde with a substituted A -cyclohexenone auto-condensation product of acetone of wherein m is an integer of at least 4 and n=3m but is not greater than 30, said heating being ef-' fected with the reactants in the presence of an alkali metal hydroxide and sufficient methyl alcohol to render the reaction mixture homogeneous at least when first heated. and subsequently heating the formed resin which has been freed of the condensing catalyst at a temperature of 150 C. to 250 C. whereby the softening point of the resin is increased.

6. A process for the production of ketone resins which comprises heating xylitone with formaldehyde in the presence of sodium hydroxide. and sufiicient methyl alcohol to render the reaction mixture homogeneous at least when first heated.

7. A process for the production of ketone resins which comprises heating xylitone with formaldehyde in the presence of sodium hydroxide and sufficient methyl alcohol to render the reaction mixture homogeneous at least when first heated, and subsequently heating the formed resin which has been freed of the condensing agent at a tem- C. to 250 C. whereby the softening point is increased above that of the initially formed resin.

8. A process for the production of ketone resins which comprises heating formaldehyde with a substituted A -cyclohexenone auto-condensation product of methyl ethyl ketone of the formula C1|H2(3m+1)0 wherein m is an integer of 4 to 10 and n=4m.

9. A process for the production of ketone resins which comprises heating a substituted A cyclohexenone product of crotonaldehyde-type autocondensation of mesityl oxide containing not more than 30 carbon atoms with an aldehyde wherein the aldehyde group is linked directly to -a member of the class consisting of the hydrogen atom and monovalent hydrocarbon radicals in the presence of a basic-acting condensation agent and sufllcient organic homogenizing solvent to render the reaction mixture homogeneous at least when first heated.

10. A process for the production of ketone resins which comprises heating a substituted ii -cyclohexenone product of crotonaldehyde-type autocondensation of mesityl oxide with formaldehyde in the presence of an alkali metal hydroxide and sufilcient methanol to render the reaction mixture homogeneous at least when first heated.

11. A thermoplastic ketone resin from the reaction at an elevated temperature in the presence of a condensing agent of a substituted A cyclohexenone with an aldehyde wherein the aldehyde group is linked directly to a member of the class consisting of the hydrogen atom and monovalent hydrocarbon radicals, said substituted A=-cyclohexenone being an auto-condensation product of an aliphatic ketone and of the formula Gamma-mp wherein m and k are integers with mof4to andkof3to9 andn=kxm.

12. A thermoplastic ketone resin from the rethe formula CnHll(2m+l)O- action at an elevated temperature in the presence of a condensing agent of a substituted ii -cyclohexenone with formaldehyde, said substituted n -cyclohexenone being an auto-condensation product of an aliphatic ketone and of the formula CnH (m(k-l)+1o wherein m and k are integers with m of at least 4 and k of at least 3 and n=-k m but not more than 30.

13. A thermoplastic ketone resin from the reaction at an elevated temperature in the presence of a condensing agent of an aldehyde wherein the aldehyde group is linked directly to a member of the class consisting of the hydrogen atom and monovalent hydrocarbon radicals with a substituted A' -cyclohexenone auto-condensation product of acetone of the formula CnH2(2m+l)O wherein m is an integer of 4 to 10 and n=3m.

14. A thermoplastic ketone resin from the reaction at an elevated temperature in the presence of a condensing agent of formaldehyde with a substituted n -cyclohexenone auto-condensation product of acetone of the formula C1|H2(21n+l)0 wherein m is an integer of at least 4 and n=-3m but is not greater than 30.

15. A thermoplastic ketone resin from the reaction at an elevated temperature in the presence of a condensing agent of formaldehyde with xylitone.

16. A thermoplastic ketone resin from the reaction at an elevated temperature in the presence of a condensing agent of formaldehyde with a substituted n -cyclohexenone auto-condensation product of methyl ethyl ketone of the formula CflHlGflH-DO wherein m is an integer of 4 to 10 and n=4m.'

17. A thermoplastic ketone resin from the reaction at an elevated temperature in the presence of a condensing agent of formaldehyde with a homoxylitone of methyl ethyl ketone.

18. A thermoplastic ketone resin from the reaction at an elevated temperature in the presence of a condensing agent of an aldehyde wherein the aldehyde group is linked directly to a member of the class consisting of the hydrogen atom and monovalent hydrocarbon radicals with a substituted n -cyclohexenone containing at least two olefinic double bonds and not more than 30 carbop; atoms per molecule obtained by crotonaldehyde-type auto-condensation of mesityl oxide.

19. A thermoplastic ketone resin from the reaction at an elevated temperature in the presence of a condensing agent of a substituted n -cyclohexenone from crotonaldehydetype auto-condensation of mesityl oxide containing at least two olefinic double bonds and not more than 30 carbon atoms per molecule with a lower aliphatic aldehyde.

20. A thermoplastic ketone resin from the reaction at an elevated temperature in the presence of a condensing agent of formaldehyde with a crotonaldehyde-type auto-condensation product of mesityl oxide containing at least two olefinic double bonds and not more than 30 carbon atoms per molecule which is a substituted N-cyclohex'enone.

VERNON n mum. 

